A facile thermal decomposing method has been developed for the fabrication of Co(x)P nanostructures with controlled size, phase, and shape (e.g., Co(2)P rod and spheres, CoP hollow and solid particles). An amorphous carbon layer could be introduced by the carbonization of organic surfactants from the precursors. The electrochemical performance of typical CoP and Co(2)P samples as anode materials has been investigated and the CoP hollow nanoparticle with carbon coating layer depicts good capacity retention and high rate capability (e.g., specific capacity of 630 mA h g(-1) at 0.2 C after 100 cycles, and a reversible capacity of 256 mA h g(-1) can be achieved at a high current rate of 5 C).